WO2021106650A1 - Matériau composite renforcé par des fibres et structure sandwich - Google Patents

Matériau composite renforcé par des fibres et structure sandwich Download PDF

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Publication number
WO2021106650A1
WO2021106650A1 PCT/JP2020/042587 JP2020042587W WO2021106650A1 WO 2021106650 A1 WO2021106650 A1 WO 2021106650A1 JP 2020042587 W JP2020042587 W JP 2020042587W WO 2021106650 A1 WO2021106650 A1 WO 2021106650A1
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Prior art keywords
fiber
composite material
reinforced composite
less
reinforced
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PCT/JP2020/042587
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English (en)
Japanese (ja)
Inventor
今井直吉
篠原光太郎
本間雅登
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東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2020567173A priority Critical patent/JP7548017B2/ja
Priority to EP20892243.5A priority patent/EP4067033A4/fr
Priority to CN202080082191.4A priority patent/CN114761213B/zh
Priority to US17/778,073 priority patent/US12076943B2/en
Publication of WO2021106650A1 publication Critical patent/WO2021106650A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
    • B29C70/14—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/22—Corrugating
    • B29C53/24—Corrugating of plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/721—Fibre-reinforced materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
    • B29C70/0035—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties comprising two or more matrix materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/081—Combinations of fibres of continuous or substantial length and short fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D99/00—Subject matter not provided for in other groups of this subclass
    • B29D99/0089—Producing honeycomb structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/28—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer comprising a deformed thin sheet, i.e. the layer having its entire thickness deformed out of the plane, e.g. corrugated, crumpled
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/253—Preform
    • B29K2105/256—Sheets, plates, blanks or films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2307/00—Use of elements other than metals as reinforcement
    • B29K2307/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0094—Geometrical properties
    • B29K2995/0096—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/002—Panels; Plates; Sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs

Definitions

  • the present invention relates to a fiber-reinforced composite material that has both light weight and mechanical properties.
  • Fiber-reinforced composite materials that use thermosetting resin or thermoplastic resin as a matrix and combine them with reinforcing fibers such as carbon fiber and glass fiber are lightweight, yet have mechanical properties such as strength and rigidity, flame retardancy, and corrosion resistance. Due to its superiority, it has been applied in many fields such as aerospace, automobiles, railroad vehicles, ships, civil engineering and construction, electronic equipment, industrial machinery, and sporting goods. On the other hand, from the viewpoint of improving fuel efficiency and portability, further weight reduction is required for members and housings, and porous fiber-reinforced composite materials having pores formed inside have also been developed. However, such a porous fiber-reinforced composite material has a problem that the mechanical properties are dramatically lowered as the proportion of pores is increased for the purpose of weight reduction. For this reason, there has been a demand for a technique for achieving both mechanical properties while reducing the weight of the fiber-reinforced composite material.
  • Patent Document 1 discloses a composite structure having reinforcing fibers, a resin, pores, and a protrusion for reinforcement.
  • Patent Document 2 shows a core structure having a zigzag cross section composed of a cured resin and a non-woven sheet.
  • Patent Document 3 discloses a structure made of paper containing carbon fibers having different diameter cross sections, and a core structure obtained by folding the structure so as to have a zigzag cross section.
  • Patent Document 1 is a technique for reducing the weight by increasing the total amount of fine pores, and has a problem that the mechanical properties are greatly deteriorated according to the weight reduction.
  • a reinforcing structure such as a rib or a boss is adopted, but this is a reinforcing structure arranged on the surface of the composite structure, which requires a specific molding mold and has a problem in terms of thinning.
  • the resin is impregnated without controlling the diameter and amount of the pores, and in the zigzag structure, the zigzag structure is opened by the load in the bending direction. It was easy and insufficient to achieve both weight reduction and mechanical properties.
  • An object of the present invention is to provide a fiber-reinforced composite material having both light weight and mechanical properties.
  • the present invention for solving such a problem includes a resin (A) and a reinforcing fiber (B), and has an in-plane oriented portion having an average fiber orientation angle of 0 ° or more and 45 ° or less of the reinforcing fiber (B) and reinforcement.
  • the fiber reinforced structure portion having an out-of-plane orientation portion having an average fiber orientation angle of the fiber (B) of more than 45 ° and 90 ° or less and the in-plane orientation portion and the out-of-plane orientation portion of the fiber reinforced structure portion.
  • Schematic diagram showing an embodiment of the fiber-reinforced composite material of the present invention Schematic diagram of an enlarged embodiment of a fiber reinforced structure portion for partitioning a cavity portion of the fiber reinforced composite material of the present invention.
  • FIG. 7 is an enlarged schematic cross-sectional view of a part of the prepreg of the embodiment shown in FIG. Enlarged schematic view of the periphery of the reinforcing fiber base material (B') in one embodiment of the prepreg. Schematic diagram showing the folded state of the reinforcing fiber base material (B') in the prepreg produced in Example 1. Schematic diagram showing the folded state of the reinforcing fiber base material (B') in the prepreg produced in Comparative Example 1.
  • FIG. 7 is an enlarged schematic cross-sectional view of a part of the prepreg of the embodiment shown in FIG. Schematic diagram showing an embodiment of the fiber-reinforced composite material of the present invention. Schematic diagram showing an embodiment of the fiber-reinforced composite material produced in Comparative Examples 1 and 3.
  • the fiber-reinforced composite material of the present invention contains a resin (A) and a reinforcing fiber (B), and has an in-plane oriented portion in which the average fiber orientation angle of the reinforcing fiber (B) is 0 ° or more and 45 ° or less, and the reinforcing fiber ( B) is partitioned by a fiber reinforced structure having an out-of-plane orientation portion having an average fiber orientation angle of more than 45 ° and 90 ° or less, and the in-plane orientation portion and the out-of-plane orientation portion of the fiber reinforced structure portion. It is composed of a hollow part.
  • FIG. 1 is a schematic view showing an embodiment of the fiber-reinforced composite material of the present invention together with an enlarged image of the fiber-reinforced structural portion.
  • the fiber reinforced structure portion 6 contains the resin (A) 2 and the reinforcing fiber (B) 3.
  • the fiber reinforced structure portion 6 also includes a microporous 5.
  • FIG. 3 is a schematic cross-sectional view of the fiber-reinforced composite material of the embodiment of FIG. 1 in a cross section orthogonal to the extending direction of the cavity.
  • FIG. 2 is an enlarged schematic view of an embodiment of the fiber reinforced structure portion for partitioning the cavity portion.
  • the "cross section" of the fiber-reinforced composite material refers to a cross section orthogonal to the extending direction of the cavity. That is, the space portion of the fiber-reinforced composite material of the present invention extends.
  • the hollow portion exists as a tunnel-like space surrounded by the fiber reinforced structure portion.
  • the average value of the maximum lengths of the cross-sectional openings of the hollow portion exceeds 500 ⁇ m.
  • the maximum length of the cross-sectional opening is the maximum length that can be drawn in a straight line in the opening in the cross section of the fiber-reinforced composite material.
  • the average value of the maximum length of the cross-sectional opening of the cavity is preferably 1000 ⁇ m or more and 10000 ⁇ m or less, more preferably 1500 ⁇ m or more and 6500 ⁇ m or less, and further preferably 2500 ⁇ m or more and 4500 ⁇ m or less.
  • the opening of the cavity is shown as a substantially triangular shape in which three sides are surrounded by the fiber reinforced structure.
  • the opening of the cavity portion is shown as a substantially trapezoidal shape having three sides formed by the fiber reinforced structure portion.
  • the cavity portion of the present invention is surrounded by the fiber reinforced structure portion, but the substantially trapezoidal cavity portion in which the opening is composed of three sides by the fiber reinforced structure portion, that is, one side.
  • the fiber reinforced structure portion has an in-plane orientation portion having an average fiber orientation angle of 0 ° or more and 45 ° or less and an average fiber orientation angle of more than 45 ° 90.
  • the cavity portion of the present invention is preferably surrounded by a fiber reinforced structure portion.
  • the shape of the cross-sectional opening of the cavity is not particularly limited, but a substantially polygonal shape or a substantially elliptical shape (including a substantially circular shape) is preferable, and a substantially triangular shape or a substantially circular shape is more preferable.
  • the fiber-reinforced structural portion has an in-plane oriented portion and an out-of-plane oriented portion in which the fiber orientation of the reinforcing fiber (B), that is, the average fiber orientation angle is different, and the cavity portion is the in-plane oriented portion and the surface. It is separated from the outer orientation part.
  • the average fiber orientation angle is assumed to be a reference line (0 °) in the in-plane direction in the cross section of the fiber-reinforced composite material, and when the reinforcing fibers intersecting the reference line are focused on, the reference line and the said This is the arithmetic average value of the acute angle formed by the reinforcing fibers.
  • the method of determining whether the part with the fiber reinforced structure part is the in-plane oriented part or the out-of-plane oriented part is as follows. As shown in FIG. 2, first, the arithmetic mean value of the thickness 7 of the fiber-reinforced composite material observed in the cross section is obtained, and a square grid having a length of 1/5 of the arithmetic mean value of the thickness 7 as one side.
  • the fiber reinforced structure is divided into two parts.
  • the cross section of the fiber reinforced structure portion divided in this way is referred to as a “divided cross section”.
  • the average fiber orientation angle is measured while moving the reference line in the thickness direction for each divided cross section, and the portion having the divided cross section having the average fiber orientation angle of 0 ° or more and 45 ° or less is the in-plane orientation portion, 45.
  • the portion having a divided cross section larger than ° and 90 ° or less is defined as an out-of-plane orientation portion.
  • the divided cross section 6A of one fiber-reinforced structure portion divided as described above is obtained, and the average fiber orientation angle is obtained for the divided cross section, and the divided cross section is either the in-plane oriented portion or the out-of-plane orientation portion. Determine if it is an oriented part.
  • the cavity portion is a space partitioned by the in-plane oriented portion and the out-plane oriented portion identified as described above.
  • the cavity faces one or more in-plane oriented portions and one or more out-of-plane oriented portions.
  • the hollow portion is preferably partitioned by an in-plane orientation portion having an average fiber orientation angle of 0 ° or more and 30 ° or less, and more preferably partitioned by an in-plane orientation portion having an average fiber orientation angle of 0 ° or more and 15 ° or less. preferable.
  • the hollow portion is preferably partitioned by an out-of-plane orientation portion having an average fiber orientation angle of 60 ° or more and 90 ° or less, and is partitioned by an out-of-plane orientation portion of 75 ° or more and 90 ° or less. Is more preferable.
  • the cavity is preferably partitioned by an in-plane orientation portion having an average fiber orientation angle of 0 ° or more and 30 ° or less and an out-plane orientation portion having an average fiber orientation angle of 60 ° or more and 90 ° or less. It is more preferable that the fibers are partitioned by an in-plane orientation portion having an average fiber orientation angle of 0 ° or more and 15 ° or less and an out-plane orientation portion having an average fiber orientation angle of 75 ° or more and 90 ° or less.
  • the cavity is preferably partitioned only by an in-plane orientation portion having an average fiber orientation angle of 0 ° or more and 30 ° or less and an out-plane orientation portion having an average fiber orientation angle of 60 ° or more and 90 ° or less. It is more preferable that the fibers are partitioned only by the in-plane orientation portion having an average fiber orientation angle of 0 ° or more and 15 ° or less and the out-plane orientation portion having an average fiber orientation angle of 75 ° or more and 90 ° or less.
  • the cross-sectional areas of the in-plane oriented portion and the out-plane oriented portion can be known.
  • the same judgment and cross-sectional area measurement are performed for all the divided cross sections in the observed image, and the sum is obtained for each of the in-plane oriented portion and the out-plane oriented portion, so that the in-plane occupying the observed image of the fiber-reinforced composite material is in-plane.
  • the cross-sectional area of the oriented portion and the cross-sectional area of the out-of-plane oriented portion can be obtained.
  • the cross-sectional area of the out-of-plane oriented portion of the fiber-reinforced structural portion is preferably 0.5 times or more and 10 times or less the cross-sectional area of the in-plane oriented portion. It is more preferably 6 times or more and 2 times or less, and further preferably 0.6 times or more and 0.8 times or less. Within this range, a reinforcing effect can be obtained in both the in-plane direction and the out-of-plane direction, and both weight reduction due to the cavity and suppression of deformation of pores can be achieved, and weight reduction and deterioration of mechanical properties can be suppressed. It is preferable because it can be compatible at a high level.
  • the resin (A) constituting the matrix of the fiber reinforced structure may be a thermoplastic resin or a thermosetting resin, but it is preferably a thermoplastic resin.
  • the resin (A) is a thermosetting resin, it is excellent in heat resistance, but it may not be preferable if the resin (A) is cured by the manufacturing method using a prepreg described later.
  • the prepreg is composed of a resin (A) and a reinforcing fiber base material (B') which is a sheet-shaped reinforcing fiber (B).
  • the prepreg reinforcing fiber base material (B) The restoring force of the folding structure of') may not be exhibited.
  • the resin (A) as a thermoplastic resin, the resin (A) can be stably melted and softened in heat molding, and a fiber-reinforced composite material having excellent light weight can be obtained, which is preferable.
  • thermoplastic resin examples include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polyethylene, polypropylene, polybutylene and modified polypropylene, polyamides such as polyoxymethylene, polyamide 6 and polyamide 66, polycarbonate and poly.
  • Polyetherene sulfide such as methyl methacrylate, polyvinyl chloride and polyphenylene sulfide, polyetherene ether, modified polyphenylene ether, polyimide, polyamideimide, polyetherimide, polysulfone, modified polysulfone, polyethersulfone, polyketone, polyetherketone, polyether.
  • thermoplastic resins examples thereof include polyarylene ether ketone such as ether ketone and polyether ketone ketone, polyarylate, polyether nitrile, and phenoxy resin. Further, these thermoplastic resins may be copolymers, modified products, and / or resins in which two or more kinds are blended.
  • the thermoplastic resin is polyolefin, polycarbonate, polyester, polyarylene sulfide, polyamide, polyoxymethylene, polyetherimide, polyethersulfone, polyarylene ether. It is more preferably at least one selected from the group consisting of ketones, and even more preferably polypropylene from the viewpoint of productivity and cost.
  • the resin (A) may further contain other fillers and additives as appropriate, depending on the intended use and the like, as long as the object of the present invention is not impaired.
  • inorganic fillers flame retardants, conductivity-imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, anti-vibration agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, heat stabilizers, mold release agents.
  • Antistatic agents plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, coupling agents and the like.
  • the melting point of the thermoplastic resin used as the resin (A) is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 120 ° C. or higher and 300 ° C. or lower, and further preferably 140 ° C. or higher and 250 ° C. or lower. It is preferable to set the temperature in this range because the moldability into the fiber-reinforced composite material and the heat resistance of the obtained fiber-reinforced composite material can be compatible with each other.
  • the glass transition temperature of the thermoplastic resin used as the resin (A) is preferably 0 ° C. or higher and 250 ° C. or lower, more preferably 50 ° C. or higher and 200 ° C. or lower, and further preferably 100 ° C. or higher and 160 ° C.
  • the resin (A) is an amorphous thermoplastic resin
  • the moldability of the thermoplastic resin into a fiber-reinforced composite material and the heat resistance of the obtained fiber-reinforced composite material can be improved by setting the temperature within the glass transition temperature of the thermoplastic resin. It is preferable because it is compatible.
  • the reinforcing fiber (B) examples include carbon fiber, glass fiber, metal fiber, aromatic polyamide fiber, polyaramid fiber, alumina fiber, silicon carbide fiber, boron fiber, and genbuiwa fiber. These may be used alone or in combination of two or more as appropriate.
  • the reinforcing fiber (B) is preferably a carbon fiber from the viewpoint of being excellent in light weight and mechanical properties.
  • the reinforcing fiber (B) preferably has an elastic modulus of 200 GPa or more. Further, as the reinforcing fiber, carbon fiber is preferable, and carbon fiber having an elastic modulus of 200 GPa or more is particularly preferable.
  • the reinforcing fiber (B) is preferably a discontinuous fiber, more specifically, the number average fiber length is preferably 1 mm or more and 50 mm or less, and the number average fiber length is 3 mm or more and 20 mm or less. It is more preferable that it is 4 mm or more and 10 mm or less. Within such a range, it becomes easy to widen the interval between the reinforcing fibers (B), and it becomes easy to control the formation of microporous fibers, which is preferable. Further, in the fiber reinforced structure portion, it is preferable that the discontinuous fibers are randomly dispersed. Since the discontinuous fibers are randomly dispersed, a fiber-reinforced composite material having a small concentration unevenness between the resin (A) and the reinforcing fibers (B) and having excellent isotropic properties can be obtained.
  • the fiber-reinforced structural portion 6 contains the reinforcing fiber (B) 3 and the resin (A) 2 as a matrix, and has a large number of microporous 5 in the resin (A) 2. It is preferable to do so. It should be noted that the fiber-reinforced structure portion does not have to have microporous as a whole, and it is sufficient that the fiber-reinforced structure portion has microporous formation in the region where the reinforcing fiber (B) exists. For example, as shown in FIG.
  • both (a region in which the reinforcing fiber (B) 3 exists and a region consisting of only the resin (A) 2) are referred to as a fiber-reinforced structural portion, but the latter is composed of only the resin (A) 2.
  • the region does not have to be microporous.
  • the fiber reinforced structure portion is impregnated with the resin (A) between the networks composed of the reinforcing fibers (B), and is contained in the resin (A) between the reinforcing fibers (B). It is preferable to have microporous. With such a structure, the weight of the porous body can be reduced, and the reinforcing effect of the reinforcing fibers (B) can be exhibited.
  • the fiber-reinforced structure preferably has microporous properties with an average pore diameter of 500 ⁇ m or less as measured by the mercury intrusion method.
  • the average pore diameter is preferably 200 ⁇ m or less, more preferably 10 ⁇ m or more and 150 ⁇ m or less, and further preferably 30 ⁇ m or more and 100 ⁇ m or less. If the average pore diameter is too small, the weight reduction effect may not be sufficient, and if it is too large, the mechanical properties may deteriorate.
  • the mercury injection method is a method for measuring the pore size using a mercury injection porosimeter.
  • Mercury is injected into a sample at a high pressure, and the pore size can be obtained from the applied pressure and the amount of injected mercury.
  • the specific gravity of the fiber-reinforced structure portion is preferably 0.3 g / cm 3 or more and 0.8 g / cm 3 or less, and 0.4 g / cm 3 or more and 0.7 g / cm 3 or less. More preferably. If it is smaller than this range, the mechanical properties may deteriorate, and if it is larger than this range, the weight reduction effect may be insufficient.
  • the specific gravity here is a value obtained by dividing the mass [g] of the sample obtained by cutting out only the fiber-reinforced structure part by the volume [cm 3 ] obtained from the sample shape, and the specific gravity measured with five randomly selected samples. It is the arithmetic mean value of.
  • the fiber-reinforced composite material as a whole preferably has a specific gravity of 0.001 g / cm 3 or more and 0.2 g / cm 3 or less, and 0.01 g / cm 3 or more and 0.15 g / cm 3 or less. More preferably, it is 0.01 g / cm 3 or more and 0.1 g / cm 3 or less. If it is smaller than this range, the mechanical properties may be insufficient. If it is larger than this range, the weight reduction effect may be insufficient. When the specific gravity is 0.1 g / cm 3 or less, it is generally particularly difficult to develop mechanical properties, and the effects of the present invention can be efficiently exhibited, which is preferable.
  • the specific gravity here is a value obtained by dividing the sample mass [g] by the volume [cm 3] obtained from the sample shape.
  • the reinforcing fibers (B) are preferably 10 parts by mass or more and 100 parts by mass or less, and the reinforcing fibers (B). Is more preferably 20 parts by mass or more and 50 parts by mass or less. If it is smaller than this range, the reinforcing effect of the reinforcing fiber (B) may be insufficient. If it is larger than this range, the weight reduction effect of the reinforcing fiber (B) may be insufficient.
  • the thickness of the fiber-reinforced composite material is preferably 0.1 mm or more and 5 mm or less, and more preferably 0.6 mm or more and 3 mm or less. Within such a range, the effect of the present invention, which is lightweight and has excellent mechanical properties even if it is thin, can be efficiently exhibited, which is preferable.
  • fiber-reinforced composite materials having pores tend to be difficult to maintain pressure in a process of crimping other materials such as a pressing process.
  • the fiber-reinforced composite material of the present invention which achieves both light weight and mechanical properties by controlling the pores, is preferable because it can be suitably applied to such a crimping process.
  • the fiber-reinforced composite material of the present invention preferably has a structure in which the openings of the cavities are aligned in the in-plane direction in the cross section, and further, a laminated structure in which a plurality of layers having such a structure are laminated. May have. Having such a laminated structure is preferable because a thick-walled or uneven-walled molded product can be easily obtained. Further, it is more preferable that the layers in which the openings are aligned in the in-plane direction have a laminated structure in which the cavities are laminated while changing the extending direction of the cavities for each layer, and the extending directions of the cavities are orthogonal to each layer.
  • the number of layers is preferably 2 layers or more and 50 layers or less, and more preferably 2 layers or more and 10 layers or less.
  • the laminating method is not particularly limited, and examples thereof include a method of heating the prepreg after laminating and a method of laminating a fiber-reinforced composite material which has been preheated and molded.
  • a method of heating the prepreg after laminating and a method of laminating a fiber-reinforced composite material which has been preheated and molded.
  • bonding between the layers during lamination and bonding with an adhesive, heat welding, or the like can be exemplified.
  • the fiber-reinforced composite material of the present invention having an excellent expansion force is preferable because it has an excellent ability to retain pores even in a heat-pressurizing process during heat welding.
  • the fiber-reinforced composite material of the present invention has a sandwich structure in which skin layers made of different fiber-reinforced resins are arranged on both sides thereof.
  • the skin layer is a layer having a higher elastic modulus than the fiber reinforced composite material.
  • the method of joining the skin layers is not particularly limited, and examples thereof include joining with an adhesive and heat welding.
  • the fiber-reinforced composite material of the present invention having excellent expansion force and its laminate, which will be described later, are preferable because they have excellent ability to retain pores even in the heat and pressurization process during heat welding.
  • the same type of reinforcing fiber as the above-mentioned reinforcing fiber (B) can be preferably used, and carbon fiber is preferable from the viewpoint of light weight, mechanical properties, and economy.
  • the reinforcing fibers constituting the fiber-reinforced resin of the skin layer preferably have a number average fiber length of 100 mm or more, and preferably 150 mm or more.
  • the upper limit of the length of the reinforcing fibers is not particularly limited, and the reinforcing fibers may be continuous over the entire width of the skin layer in the fiber orientation direction, or may be divided in the middle.
  • the skin layer is a fiber-reinforced resin layer in which reinforcing fibers are arranged in one direction, while changing the stacking angle, that is, changing the arrangement direction of the reinforcing fibers in each layer.
  • the resin contained in the fiber reinforced resin of the skin layer is preferably a thermosetting resin.
  • the thermosetting resin include unsaturated polyester resin, vinyl ester resin, epoxy resin, phenol resin, urea resin, melamine resin, thermosetting polyimide resin, cyanate ester tree, bismaleimide resin, benzoxazine resin, or these. There are copolymers, modified products, and resins blended with at least two of these. Among them, as the thermosetting resin, an epoxy resin having excellent mechanical properties, heat resistance, and adhesiveness to reinforcing fibers is preferable.
  • the fiber-reinforced composite material of the present invention is, for example, a prepreg in which a resin (A) is impregnated with a reinforcing fiber base material (B') which is a sheet-shaped reinforcing fiber (B), and is a reinforcing fiber base material.
  • B' heats a prepreg existing in a folded state having a plurality of folds having a folding angle of 0 ° or more and less than 90 ° in the prepreg to a temperature at which the resin (A) melts or softens, and forms the prepreg. It can be manufactured by.
  • the reinforcing fiber base material (B') When the reinforcing fiber base material (B') is folded with a folding angle of 0 ° or more and less than 90 °, the crease tries to be stretched, that is, the folding angle is expanded, in an attempt to return to the structure before folding.
  • the restoring force which is the force in the direction of the prepreg, is released, and the expansion force in the thickness direction of the prepreg can be obtained in the molding of the prepreg into the fiber-reinforced composite material.
  • the reinforcing fiber base material (B') in the prepreg becomes the reinforcing fiber (B) in the fiber-reinforced structural portion of the fiber-reinforced composite material through the heating and molding.
  • the folding angle in the present specification means a cross section orthogonal to the direction of the crease (hereinafter, unless otherwise specified in the present specification, the "cross section" of the prepreg means a cross section orthogonal to the direction of the crease. As shown in FIG. 5, the angle ⁇ formed by the bent portion of the reinforcing fiber base material (B') 3 centered on the crease 31.
  • the folding angle of the reinforcing fiber base material (B') is preferably 0 ° or more and 75 ° or less, more preferably 0 ° or more and 45 ° or less, further preferably 0 ° or more and 15 ° or less, and particularly preferably 1 ° or more and 5 ° or less. preferable. Within this range, the expansion force in molding into the fiber-reinforced composite material can be increased, which is preferable.
  • the first fold when an arbitrarily selected fold is used as the first fold, two folds adjacent to both sides of the first fold are used as the second fold, and the second fold is used.
  • two folds further adjacent to the outside of the second fold are counted as a third fold, and two folds further adjacent to the outside of the third fold are counted as a fourth fold, the first fold is counted.
  • the term "proximity” is used as a term for expressing a concept including the case of contact.
  • the first crease that is close to each other in this way and the nth fold that is close to the first crease are referred to, and may be simply referred to as "a pair of adjacent creases". is there.
  • the reinforcing fiber base material (B') has a substantially trapezoidal shape, the pair of folds corresponding to both ends of the shorter base corresponds to the "pair of adjacent creases".
  • the distance between the pair of adjacent folds is Lr / Lf.
  • Lf is preferably 1 mm or more and 200 mm or less.
  • Lr / Lf is more preferably 0.2 or less, and even more preferably 0.05 or less.
  • Lf is more preferably 1 mm or more and 100 mm or less, further preferably 2 mm or more and 50 mm or less, and particularly preferably 3 mm or more and 10 mm or less.
  • the pore diameter in molding into the fiber-reinforced composite material can be easily controlled, which is preferable.
  • the folded state of the reinforcing fiber base material (B') will be described with reference to a drawing that specifically illustrates the folded state of the reinforcing fiber base material (B').
  • the folded state of the reinforcing fiber base material (B') is not limited by these drawings.
  • FIG. 6 is a schematic perspective view showing only the reinforcing fiber base material (B') taken out in order to explain the folded state of the reinforcing fiber base material (B') in the prepreg in one embodiment.
  • FIG. 7 is a schematic cross-sectional view of the prepreg of the same embodiment, and
  • FIG. 8 is a schematic cross-sectional view in which a part thereof is further enlarged.
  • the reinforcing fiber base material (B') has a first crease and a second crease adjacent to the first crease when an arbitrarily selected fold is used as the first crease in the cross section. It is in a folded state including a Z-shaped structure having one of the folds as a bending point.
  • the reinforcing fiber base material (B') has the first crease and the second crease adjacent to the first crease in the cross section. It is folded so as to form a Z-shaped structure having the crease indicated by 31B of one of the folds as a bending point.
  • the reinforcing fiber base material (B') has two creases adjacent to both sides of the first crease as the first crease in the cross section.
  • the crease, the two folds further adjacent to the outside of the second fold are referred to as the third fold, and the two folds further adjacent to the outside of the third fold are referred to as the fourth fold.
  • It has a fold structure including a substantially triangular structure formed by the proximity of one fold and one of the fourth folds. For example, assuming that the fold shown by 31A in FIG. 8 is the first fold, one of the second folds is 31B, one of the third folds is 31C, and one of the fourth folds is 31D.
  • the reinforcing fiber base material (B') has a fold structure including a substantially triangular structure formed by the proximity of the first fold 31A and the fourth fold 31D.
  • the first crease 31A and the fourth crease 31D may be in contact with each other or may be separated from each other to some extent. That is, according to the above description, in the present embodiment, the crease 31A and the crease 31D are a pair of creases that are close to each other. In the former case, the contact point between the first fold 31A and the fourth fold 31D, the second fold 31B, and the third fold 31C form a substantially triangular structure, and in the latter case, the first fold 31A.
  • a substantially triangular structure having one end opened is formed by the separation of the fourth fold 31D and the fourth crease 31D.
  • substantially triangular is used as a term that includes such a structure. With such a folding structure, a force for the substantially triangular structure to extend vertically is generated, and a restoring force can be obtained.
  • the reinforcing fiber base material (B') has a continuous folding structure while the folding structure including the substantially triangular structure is inverted. Having such a regular folding structure makes it easy to control the expansion force in a desired direction. Not limited to this embodiment, it is preferable that the reinforcing fiber base material (B') has a regular folding structure over the entire prepreg in order to obtain a uniform expansion force.
  • the linear distance between the first fold and the fourth fold adjacent to the first fold is Lr
  • the reinforcing fiber base material (B') is from the first fold to the fourth fold.
  • Lr / Lf is 0.3 or less and Lf is 1 mm or more and 200 mm or less.
  • Lr is the shortest distance between the surfaces of the reinforcing fiber base materials (B') in a pair of adjacent creases.
  • Lf corresponds to the length of the reinforcing fiber base material (B') between a pair of adjacent folds, that is, from the first fold 31A to the fourth fold 31D in FIG.
  • Lr / Lf is preferably 0.2 or less, more preferably 0.05 or less.
  • Lf is more preferably 1 mm or more and 100 mm or less, further preferably 2 mm or more and 50 mm or less, and particularly preferably 3 mm or more and 10 mm or less.
  • the distance Lf connected from the first fold to the fourth fold along the reinforcing fiber base material (B') is defined.
  • Ls be the linear distance between the second crease and the first crease existing in the direction opposite to the measurement direction.
  • the Lr and Ls are alternately continuous along the surface of the prepreg. For example, assuming that the fold shown by 31A in FIG. 12 is the first fold, one of the second folds is 31B, one of the third folds is 31C, and one of the fourth folds is 31D.
  • the reinforcing fiber base material (B') has a fold structure including a substantially triangular structure in a cross section formed by the proximity of the first fold 31A and the fourth fold 31D. ..
  • the linear distance between the other 31E and 31A of the second crease is Ls.
  • Ls is preferably 0.1 mm or more and 50 mm or less, more preferably 1 mm or more and 10 mm or less, and further preferably 2 mm or more and 5 mm or less. Further, Lr / Ls is preferably 0 or more and less than 0.8, more preferably 0 or more and 0.3 or less, and further preferably 0 or more and 0.2 or less. Within such a range, in the fiber-reinforced composite material obtained by expanding the prepreg, it is possible to control the maximum length of the cross-sectional opening and the ratio of the in-plane oriented portion to the out-plane oriented portion, and it becomes possible to control the deflection under load. It is preferable because it enables control of.
  • the reinforcing fiber base material (B') is preferably a non-woven fabric composed of discontinuous reinforcing fibers (B).
  • FIG. 9 is an enlarged schematic view of an embodiment of the reinforcing fiber base material (B') contained in the above-mentioned prepreg together with the resin (A) impregnated therein.
  • the reinforcing fiber base material (B') is a non-woven fabric composed of discontinuous reinforcing fibers.
  • the reinforcing fiber base material (B') impregnated with the resin (A) and in the compressed state causes springback when the resin (A) is melted or softened and the compressed state is released. As shown in FIG.
  • this springback forms fine pores between the reinforcing fibers and in the resin (A). That is, microporous formation is formed in the reinforcing fiber base material (B').
  • the reinforcing fiber base material (B') is particularly preferably in the form of a non-woven fabric in which discontinuous reinforcing fibers (B) are randomly dispersed, and the non-woven fabric is produced by an airlaid method, a carding method, a papermaking method, or the like. It is possible.
  • FIG. 3 is a schematic cross-sectional view showing an example of a fiber-reinforced composite material molded using the prepreg shown in FIG. 7.
  • the resin (A) is melted or softened, and the restoring force of the folded structure of the reinforcing fiber base material (B') is released.
  • This restoring force becomes an expansion force in the thickness direction of the prepreg, and this expansion force forms a cavity substantially surrounded by the reinforcing fiber base material (B').
  • the folding structure of the reinforcing fiber base material is substantially the same as the folding structure in the prepreg described above, and the description of the folding structure follows the description in the prepreg described above.
  • the folding angle of the reinforcing fiber base material (B') is increased by molding.
  • the resin (A) is a resin impregnated in the reinforcing fiber base material (B'), and more specifically, the inside of the reinforcing fiber base material (B') and the above-mentioned. It is a resin impregnated in both of the spaces formed between the reinforcing fiber base materials (B') by folding the reinforcing fiber base material (B').
  • the hollow portion preferably has a structure in which between a pair of adjacent folds 31 of the reinforcing fibers (B) are bonded by the resin (A). With such a structure, when a load is applied to the fiber-reinforced composite material, deformation due to opening in a pair of adjacent creases can be suppressed.
  • the prepreg as described above can be produced by a production method having the following steps [1] and [2] in this order.
  • Step [1] A step of folding the reinforcing fiber base material (B') into a folded state having a plurality of creases;
  • Step [2] A step of compounding the resin (A) with the folded reinforcing fiber base material (B').
  • the reinforcing fiber base material (B') is folded in the above-mentioned folded state.
  • a reinforcing fiber having a high elastic modulus has a low elongation and tends to be easily broken by bending.
  • a method of directly injecting the molten resin (A) into the reinforcing fiber base material (B') examples thereof include a method in which a film-like, powder-like or fibrous resin (A) is compounded with a reinforcing fiber base material (B') and impregnated by heating and melting. From the viewpoint of ease of production, a method of applying pressure in a state of being heated to a temperature higher than the temperature at which the resin (A) melts or softens and impregnating the reinforcing fiber base material (B') is desirable.
  • a press molding machine or a double belt press machine can be preferably used as the equipment for realizing such an impregnation method.
  • a press molding machine or a double belt press machine can be preferably used.
  • productivity can be improved by using an intermittent press system in which two or more machines for heating and cooling are arranged in parallel.
  • the continuous type it is the latter, and continuous processing can be easily performed, so that continuous productivity is excellent.
  • the fiber-reinforced composite material of the present invention can be produced by heating the above-mentioned prepreg to a temperature higher than the temperature at which the resin (A) melts or softens, and molding the prepreg.
  • the resin (A) is heated to a temperature higher than the temperature at which it melts or softens and softens, the restoring force that tries to return the folded structure of the reinforcing fiber base material (B') to the structure before folding, that is, the folding angle is expanded. The force in the direction of doing is released.
  • FIG. 3 is a schematic cross-sectional view showing an example of a fiber-reinforced composite material molded using the prepreg shown in FIG. 7.
  • the prepreg is heated and the resin (A) is softened, so that the reinforcing fiber base material (B') is deformed in the direction in which the folding angle of the reinforcing fiber base material (B') is expanded, and the prepreg expands. To do.
  • the prepreg is heated and the resin (A) is softened, so that the reinforcing fiber base material (B') is deformed in the direction in which the folding angle of the reinforcing fiber base material (B') is expanded, and the prepreg expands.
  • FIG. 7 is a schematic cross-sectional view showing an example of a fiber-reinforced composite material molded using the prepreg shown in FIG. 7.
  • this expansion forms a fiber-reinforced structural portion having an in-plane oriented portion and an out-of-plane oriented portion, and an in-plane oriented portion and an out-of-plane orientation portion of the fiber-reinforced structure portion.
  • the hollow portion 4 partitioned by the portions is formed.
  • the temperature at which the resin (A) melts or softens may be higher than the melting point, but is 20 ° C. or higher higher than the melting point. Is preferable.
  • the resin (A) is an amorphous thermoplastic resin
  • the temperature may be higher than the glass transition temperature, but a temperature higher than the glass transition temperature by 20 ° C. or more is preferable.
  • the upper limit temperature it is preferable to apply a temperature equal to or lower than the thermal decomposition temperature of the resin (A).
  • the thickness control method does not depend on the method as long as the obtained fiber-reinforced composite material can be controlled to the desired thickness, but the thickness is directly controlled by the method of restraining the thickness by using a metal plate or the like and the adjustment of the pressing force.
  • the method or the like is preferable from the viewpoint of ease of production.
  • a press molding machine or a double belt press machine can be preferably used as the equipment for realizing such a method.
  • productivity can be improved by using an intermittent press system in which two or more machines for heating and cooling are arranged in parallel.
  • the continuous type it is the latter, and continuous processing can be easily performed, so that continuous productivity is excellent.
  • PP resin It is composed of 80% by mass of polypropylene (“Prime Polypro” (registered trademark) J105G manufactured by Prime Polymer Co., Ltd.) and 20% by mass of acid-modified polypropylene (“Admer” QB510 manufactured by Mitsui Chemicals, Inc.), and is composed of JIS K7121 (2012).
  • Such a polypropylene resin composition was prepared as a resin pellet in which polypropylene, which is a thermoplastic resin, and acid-modified polypropylene were mixed as raw materials in the above mass ratio and melt-kneaded by a twin-screw extruder having a cylinder temperature of 200 ° C. Further, the resin pellets were press-molded using a press molding machine adjusted to have a mold surface temperature of 180 ° C. and a film thickness of 0.22 mm to prepare a PP resin film having a grain size of 200 g / cm 2.
  • PC resin Amorphous polycarbonate resin made of polycarbonate (“Iupilon” (registered trademark) H-4000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and having a glass transition temperature of 150 ° C. measured in accordance with JIS K7121 (2012) is used. There was. Polycarbonate resin pellets, which are thermoplastic resins, are press-molded using a press molding machine adjusted to have a mold surface temperature of 240 ° C. and a film thickness of 0.17 mm to prepare a PC resin film having a grain size of 200 g / cm 2. did.
  • Carbon fiber non-woven fabric A copolymer containing polyacrylonitrile as a main component was spun, fired, and surface-oxidized to obtain a carbon fiber bundle having a total number of single yarns of 12,000.
  • the characteristics of this carbon fiber bundle were that the tensile elastic modulus measured in accordance with JIS R7608 (2007) was 220 GPa, and the single fiber had a circular cross section with a diameter of 7 ⁇ m.
  • the carbon fiber bundle was cut into a length of 6 mm with a cartridge cutter to obtain chopped carbon fiber.
  • a dispersion liquid having a concentration of 0.1% by mass consisting of water and a surfactant (polyoxyethylene lauryl ether (trade name) manufactured by Nakaraitex Co., Ltd.) was prepared, and this dispersion liquid and chopped carbon fiber were used.
  • a carbon fiber base material was prepared.
  • the manufacturing apparatus includes a cylindrical container having a diameter of 1000 mm having an opening / closing cock at the bottom of the container as a dispersion tank, and a linear transport portion (inclination angle of 30 °) connecting the dispersion tank and the paper making tank.
  • a stirrer is attached to the opening on the upper surface of the dispersion tank, and chopped carbon fibers and a dispersion liquid (dispersion medium) can be charged through the opening.
  • the papermaking tank is provided with a mesh conveyor having a papermaking surface having a width of 500 mm at the bottom, and a conveyor capable of transporting a carbon fiber base material (papermaking base material) is connected to the mesh conveyor. Papermaking was carried out with the carbon fiber concentration in the dispersion liquid being 0.05% by mass.
  • the paper-made carbon fiber base material was dried in a drying oven at 200 ° C. for 30 minutes to obtain a carbon fiber non-woven fabric in which the orientation directions of the single yarns of the carbon fibers were randomly dispersed.
  • Thermosetting prepreg used for the skin layer A copolymer containing polyacrylonitrile as a main component was spun, fired, and surface-oxidized to obtain a carbon fiber bundle having a total number of single yarns of 12,000. The characteristics of this carbon fiber bundle were that the tensile elastic modulus measured in accordance with JIS R7608 (2007) was 220 GPa, and the single fiber had a circular cross section with a diameter of 7 ⁇ m.
  • Epoxy resin (“Epicoat (registered trademark)” 828:30 parts by mass, "Epicoat (registered trademark)” 1001: 35 parts by mass, “Epicoat (registered trademark)” 154: 35 parts by mass manufactured by Japan Epoxy Resin Co., Ltd.
  • Polyvinylformal (“Vinirec (registered trademark)” K manufactured by Chisso Co., Ltd.): After heat-kneading 5 parts by mass with a kneader to uniformly dissolve polyvinylformal, the curing agent disiandiamide (DICY7 manufactured by Japan Epoxy Resin Co., Ltd.) ): 3.5 parts by mass and curing agent 4,4-methylenebis (phenyldimethylurea) (PITI Japan Co., Ltd. "Omicure” (registered trademark) 52): 7 parts by mass are kneaded with a kneader. The uncured epoxy resin composition was prepared. From this, an epoxy resin film having a basis weight of 132 g / m 2 was prepared using a knife coater.
  • the arithmetic mean value of the thickness is obtained from a total of 10 places of the fiber-reinforced composite material observed in the cross section, and the fiber-reinforced structure portion is formed in a square lattice having a length of 1/5 of the arithmetic mean value of the thickness as one side.
  • the cross section of was divided.
  • the angle formed by the major axis direction of the fiber ellipse and the reference direction is the reinforcing fiber (B).
  • the fiber orientation angles were measured for a total of 400 reinforcing fibers (B) for each divided cross section, and the arithmetic mean value of these was determined as the average fiber orientation angle.
  • the divided cross section having an average fiber orientation angle of 0 ° or more and 45 ° or less was defined as an in-plane oriented portion, and the divided cross section larger than 45 ° and 90 ° or less was defined as an out-of-plane oriented portion.
  • the cross-sectional area ratio of the in-plane oriented portion is obtained as a ratio (%) obtained by dividing the cross-sectional area of the in-plane oriented portion by the sum of the cross-sectional area of the in-plane oriented portion and the cross-sectional area of the out-of-plane oriented portion and multiplying by 100.
  • the cross-sectional area ratio of the out-of-plane oriented portion was obtained as a ratio (%) obtained by dividing the cross-sectional area of the out-of-plane oriented portion by the sum of the cross-sectional area of the in-plane oriented portion and the cross-sectional area of the out-of-plane oriented portion and multiplying by 100. ..
  • the ratio of the cross-sectional area of the out-of-plane oriented portion to the cross-sectional area of the in-plane oriented portion was obtained by dividing the cross-sectional area of the out-of-plane oriented portion by the cross-sectional area of the in-plane oriented portion.
  • the arithmetic average value was recalculated by matching the fiber orientation angles of the reinforcing fibers (B) in the in-plane orientation portion, and this was used as the average fiber orientation angle of the entire in-plane orientation portion. Further, the arithmetic average value was recalculated by combining the fiber orientation angles of the reinforcing fibers (B) in the out-of-plane orientation portion, and this was used as the average fiber orientation angle of the entire out-of-plane alignment portion.
  • the specific gravity of the fiber-reinforced structure is a value obtained by preparing a sample obtained by cutting out the fiber-reinforced structure from the fiber-reinforced composite material and dividing the sample mass [g] by the volume [cm 3] obtained from the outer circumference of the sample. It is obtained by the arithmetic mean value of the specific densities measured with 5 samples randomly extracted.
  • the specific gravity of the fiber-reinforced composite material can be obtained as a value obtained by dividing the mass [g] of the fiber-reinforced composite material by the volume [cm 3] obtained from the outer circumference of the fiber-reinforced composite material.
  • Example 1 As the reinforcing fiber base material (B'), a folding base material having a basis weight of 100 g / cm 2 was prepared by folding the carbon fiber non-woven fabric produced as described above so as to have the cross-sectional structure shown in FIG. At this time, when the prepreg is used, the reinforcing fiber base material (B') is folded so that the linear distance (Lr) between the adjacent pair of folds is 0 mm, that is, in contact with the adjacent pair of folds 8. The distance (Lf) of connecting the adjacent pair of folds along the carbon fiber non-woven fabric is 10 mm, and the distance (Lf) is 10 mm, and the distance (Lf) is 10 mm.
  • the carbon fiber non-woven fabric was impregnated with PP resin by pressurizing at a mold temperature of 180 ° C. and a pressure of 3 MPa for 10 minutes to obtain a prepreg having a side of 200 mm.
  • a fiber-reinforced composite material is formed by heating and expanding one of the obtained prepregs for 10 minutes using a press molding machine adjusted so that the mold surface temperature is 180 ° C. and the thickness of the molded product is 2.8 mm. did.
  • the obtained fiber-reinforced composite material had an opening having a substantially triangular cross section surrounded on three sides by a fiber-reinforced structural portion as shown in FIG. The openings of the cavities were aligned in the in-plane direction.
  • the evaluation results are shown in Table 1.
  • Example 2 As the reinforcing fiber base material (B'), processing was carried out in the same manner as in Example 1 except that the composition of the folding base material was changed so that Lr was 1 mm and Lf was 9 mm, and a prepreg and a fiber-reinforced composite material were obtained. ..
  • the obtained fiber-reinforced composite material had an opening having a substantially triangular cross section surrounded on three sides by a fiber-reinforced structural portion as shown in FIG. The openings of the cavities were aligned in the in-plane direction.
  • the evaluation results are shown in Table 1.
  • Example 3 As the reinforcing fiber base material (B'), processing was carried out in the same manner as in Example 1 except that the composition of the folding base material was changed so that Lr was 2 mm and Lf was 8 mm, and a prepreg and a fiber-reinforced composite material were obtained. ..
  • the obtained fiber-reinforced composite material had an opening having a substantially trapezoidal cross section having three sides formed by the fiber-reinforced structural portion as shown in FIG. The openings of the cavities were aligned in the in-plane direction. The evaluation results are shown in Table 1.
  • Example 4 As the reinforcing fiber base material (B'), the same folding base material as in Example 1 was used, and a PC resin film having a basis weight of 200 g / cm 2 was laminated as the resin (A) and heat-pressed. In the heat pressing step, the carbon fiber non-woven fabric was impregnated with PC resin by pressurizing at a mold temperature of 240 ° C. and a pressure of 3 MPa for 10 minutes to obtain a prepreg having a side of 200 mm. A fiber-reinforced composite material was formed by heating and expanding one of the obtained prepregs for 10 minutes using a press molding machine adjusted so that the mold temperature was 240 ° C. and the thickness of the molded product was 2.2 mm.
  • the obtained fiber-reinforced composite material had an opening having a substantially triangular cross section surrounded on three sides by a fiber-reinforced structural portion as shown in FIG.
  • the openings of the cavities were aligned in the in-plane direction.
  • the evaluation results are shown in Table 1.
  • Example 5 Two prepregs obtained in Example 1 were laminated to form a preform, and the mixture was heated for 10 minutes using a press molding machine adjusted so that the mold temperature was 180 ° C. and the thickness of the molded product was 4.8 mm. A fiber-reinforced composite material of the laminate was molded. The obtained fiber-reinforced composite material had an opening having a substantially triangular cross section surrounded on three sides by a fiber-reinforced structural portion as shown in FIG. 1, and this was a structure in which two layers were laminated. The openings of the cavities were aligned in the in-plane direction. The evaluation results are shown in Table 1.
  • Example 6 As the reinforcing fiber base material (B'), processing was carried out in the same manner as in Example 1 except that the composition of the folding base material was changed so that Lr was 3 mm and Lf was 7 mm, and a prepreg and a fiber-reinforced composite material were obtained. ..
  • the obtained fiber-reinforced composite material had an opening having a substantially trapezoidal cross section having three sides formed by the fiber-reinforced structural portion as shown in FIG. The openings of the cavities were aligned in the in-plane direction. The evaluation results are shown in Table 1.
  • Example 7 The fiber-reinforced composite material obtained in Example 1 was used for the core layer, and the thermosetting prepreg prepared as described above was arranged as a skin layer on the outside thereof, and the orientation direction of the reinforcing fibers on the surface of one skin layer was set. Based on 0 °, the layers were laminated so that the laminated structure was [0 ° / 90 ° / fiber reinforced composite material / 90 ° / 0 °]. Next, the thermosetting prepreg was cured by heating and pressing at a die temperature of 150 ° C. and a pressure of 1 MPa for 10 minutes to obtain a sandwich structure. The thickness of the fiber-reinforced composite material in the obtained sandwich structure was 2.4 mm, and the sandwich structure could be satisfactorily used as a core layer without being crushed.
  • Example 8 The fiber-reinforced composite material of the laminate obtained in Example 5 was used for the core layer, a thermosetting prepreg was arranged as a skin layer on the outside thereof, and the orientation direction of the reinforcing fibers on the surface of one skin layer was set to 0 °.
  • the layers were laminated so that the laminated structure was [0 ° / 90 ° / fiber reinforced composite material / 90 ° / 0 °].
  • the thermosetting prepreg was cured by heating and pressing at a die temperature of 150 ° C. and a pressure of 1 MPa for 10 minutes to obtain a sandwich structure.
  • the thickness of the laminated body in the obtained sandwich structure was 4.3 mm, and it could be satisfactorily used as a core layer without being crushed even when the sandwich structure was formed.
  • a base material having a basis weight of 100 g / cm 2 having creases was prepared so that the carbon fiber non-woven fabric had a cross-sectional structure having a zigzag structure apex 10 as shown in FIG. At this time, creases were made so that the repetition interval 11 between the vertices of the zigzag structure was 5 mm at equal intervals.
  • a PP resin film having a basis weight of 200 g / cm 2 was laminated on the base material and heat-pressed. In the heat pressing step, the base material was impregnated with PP resin by pressurizing at a mold temperature of 180 ° C.
  • a fiber-reinforced composite material was formed by heating and expanding one of the obtained prepregs for 10 minutes using a press molding machine adjusted so that the mold temperature was 180 ° C. and the thickness of the molded product was 2.8 mm.
  • the obtained fiber-reinforced composite material had a zigzag structure in the cross section of the fiber-reinforced structure portion 6 as shown in FIG. The evaluation results are shown in Table 1.
  • the distance between the upper and lower molds of the mold was set to 2.8 mm, and molding was performed for the purpose of forming a molded product thickness of 2.8 mm, but the prepreg did not expand to the thickness between the upper and lower molds of the mold, and was obtained. No cavities were formed in the fiber-reinforced composite material, and the thickness remained at 0.9 mm.
  • the evaluation results are shown in Table 1.
  • Example 3 As the reinforcing fiber base material (B'), processing was carried out in the same manner as in Example 1 except that the composition of the folding base material was changed so that Lr was 4 mm and Lf was 6 mm, and a prepreg and a fiber-reinforced composite material were obtained. .. The obtained fiber-reinforced composite material had a zigzag structure in the cross section of the fiber-reinforced structure portion as shown in FIG. The evaluation results are shown in Table 1.
  • thermosetting prepreg was arranged as a skin layer on the outside thereof, and the orientation direction of the reinforcing fibers on the surface of one skin layer was set as a reference.
  • the thermosetting prepregs were laminated so that the laminated structure was [0 ° / 90 ° / fiber reinforced composite material / 90 ° / 0 °].
  • the thermosetting prepreg was cured by heating and pressing at a die temperature of 150 ° C. and a pressure of 1 MPa for 10 minutes to obtain a sandwich structure.
  • the thickness of the fiber-reinforced composite material in the obtained sandwich structure was 0.6 mm, and it was crushed by the molding pressure of the sandwich structure and could not be used as the core layer.
  • the fiber-reinforced composite material of the present invention can be suitably applied to applications such as aircraft structural members, wind turbine blades, automobile structural members, IC trays, and housings for notebook computers.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Textile Engineering (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'objectif de la présente invention est d'obtenir un matériau composite renforcé par des fibres dans lequel des propriétés de légèreté et des propriétés mécaniques sont obtenues à un niveau élevé. La présente invention concerne un matériau composite renforcé par des fibres contenant une résine (A) et une fibre de renforcement (B) et ayant une structure renforcée par des fibres et des cavités, la structure renforcée par des fibres ayant des parties d'orientation dans le plan dans lesquelles l'angle moyen d'orientation des fibres de la fibre de renforcement (B) est de 0 à 45° et des parties d'orientation hors plan dans lesquelles l'angle moyen d'orientation des fibres de la fibre de renforcement (B) est supérieur à 45° et inférieur ou égal à 90°, et les cavités sont séparées par les parties d'orientation dans le plan et les parties d'orientation hors plan de la structure renforcée par des fibres.
PCT/JP2020/042587 2019-11-29 2020-11-16 Matériau composite renforcé par des fibres et structure sandwich WO2021106650A1 (fr)

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JP2020567173A JP7548017B2 (ja) 2019-11-29 2020-11-16 繊維強化複合材料およびサンドイッチ構造体
EP20892243.5A EP4067033A4 (fr) 2019-11-29 2020-11-16 Matériau composite renforcé par des fibres et structure sandwich
CN202080082191.4A CN114761213B (zh) 2019-11-29 2020-11-16 纤维增强复合材料及夹层结构体
US17/778,073 US12076943B2 (en) 2019-11-29 2020-11-16 Fiber-reinforced composite material and sandwich structure

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JPS5743833A (en) * 1980-08-29 1982-03-12 Matsushita Electric Works Ltd Formation of prepreg
JP2012500864A (ja) 2008-08-21 2012-01-12 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 高圧縮率を有する折り畳みコアおよびそれから製造された物品
JP2013511629A (ja) 2009-11-20 2013-04-04 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 炭素繊維紙に基づく折りたたみコアおよびそれから作られる物品
WO2014103711A1 (fr) * 2012-12-26 2014-07-03 東レ株式会社 Corps moulé possédant une structure creuse, et procédé de fabrication de celui-ci
US20140265043A1 (en) * 2013-03-15 2014-09-18 Bell Helicopter Textron Inc. Composite core and method of making same
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CN114761213B (zh) 2024-07-09
US20220410502A1 (en) 2022-12-29
CN114761213A (zh) 2022-07-15

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